Electrochromic device

(a) A 2.5 cm×2.5 cm transparent nanostructured semiconductor film, consisting of a 4 μm thick layer of fused TiO 2 nanocrystallites, was deposited on a 3.3 cm×3.3 cm fluorine doped tin oxide on glass substrate (15 Ω, 0.5 μm thick, Libby-Owen Ford Tec 15). A colloidal TiO 2 dispersion was prepared by hydrolysis of titanium tetraisopropoxide. The average diameter of the initially formed crystallites (7 nm) was increased by autoclaving at 200° C. for 12 hours to 12 nm. Concentrating the autoclaved dispersion to 160 g/l and adding Carbowax (Trade Mark) 20000 (40% wt. equiv. of TiO 2 ) yielded a white viscous sol. (Carbowax 20000 is an ethylene glycol polymer whose average molecular weight is 20000.). A 4 μm thick layer of the above sol was deposited using a screen printing technique on the conducting glass substrate. The resulting gel-film was dried in air for 1 h, sintered in air at 450° C. for 12 h and stored in a darkened vacuum desiccator prior to use. The resulting transparent nanostructured electrodes were 4 μm thick and had a surface roughness of about 1000.

(b) An n-type redox chromophore, bis-(2-phosphonoethyl)-4,4′-bipyridinium dichloride was prepared by adding 4,4′-bipyridine (4.4 g) and diethyl-2-ethylbromo-phosphonate (15.0 g) to water (75 ml). The reaction mixture was refluxed for 72 h and allowed to cool. Following addition of conc. hydrochloric acid (75 ml) the reaction mixture was refluxed for a further 24 h. To recover the product, the reaction mixture was concentrated, to 50 ml, isopropyl alcohol (200 ml) added drop-wise, stirred on ice for one hour and filtered. The white crystalline product was washed with cold isopropyl alcohol and air dried to give pure bis-(2-phosphonoethyl)-4,4″-bipyridinium dichloride (12.72 g, 84.24% yield). Calculated for bis-(2-phosphonoethyl)-4,4′-bipyridinium dichloride (C 14 H 20 N 2 Cl 2 O 6 P 2 ): C, 37.77; H, 4.53; N, 6.29. Found: C, 35.09; H, 4.49; N, 6.09. 1 H NMR (water-d 2 ): δ 2.31-2.43 (m, 4H); δ 4.68-4.80 (m, 4H); δ 8.33 (d, unresolved metacoupling, 4H); δ 8.94 (d, unresolved metacoupling, 4H).

(c) TiO 2 films, prepared as described above, were modified by chemisorption of a monolayer of the n-type redox chromophore, also prepared as described above, from an aqueous solution (0.02 mol.dm −3 ) over 24 h, washed with distilled isopropanol, dried in air and stored in a darkened vacuum desiccator for 48 h prior to use.

(d) A 2.5 cm×2.5 cm transparent nanostructured SnO 3 :Sb film was prepared on a 3.3 cm×3.3 cm F-doped tin oxide glass substrate (15 Ω, 0.5 μm thick, supplied by Libby-Owen Ford Tec 15) largely as described in “Specttroscopy of Highly Doped Nanostructured Tin Dioxide Electrodes” The Journal of Physical Chemistry, 1999, 103, pp 3093-3098, G. Boschloo and D. Fitzmaurice. Briefly, 10 drops of acetic acid (2.0 mol dm −3 ) were added with stirring to an aqueous dispersion (50 g) of 5 nm diameter Sb-doped SnO 2 nanocrystals (15% by wt. SnO 2 :Sb, supplied by Alfa). The gel which formed immediately was diluted by addition of water (15 ml) and autoclaved at 200° C. for 12 h. Addition of Carbowax 20000 (3.75 g) with stirring for 8 h yielded an amber viscous paste which was diluted with water (10 ml) to make it suitable for spreading. This paste was spread using a glass rod on the conducting glass substrate masked by Scotch tape. Following drying in air for 1 h the film was fired, also in air, at 450° C. for 12 h. The resulting transparent nanostructured SnO 2 :Sb films were 3.0 μm thick and had a surface roughness of about 1000.

(e) The p-type redox promoter VIII was prepared as shown in Scheme 1, as follows:

XI: β-(10-phenothiazyl) Propionitrile

Triton B (benzyl trimethylammonium hydroxide; 0.6 ml of a 40% aq. soln.) was added dropwise to a solution of phenothiazine (X, 50 g) in acrylonitrile (45 ml) on ice resulting in a vigorous reaction. The reaction mixture was refluxed for 1 h and allowed to cool. The resulting crude product was recrystallized from a 30:70 mixture of hot ethanol and acetone to yield orange crystals of XI, (31.27 g, 49.6%).

XII: β-(10-phenothiazyl) Propionic Acid

The compound XI (31.27 g) was added to a mixed solvent (350 ml methanol, 105 ml water) NaOH (35 g) solution, refluxed for 15 h and allowed to cool. The crude product was poured on ice water and acidified by the addition of sulphuric acid (2 mol dm −3 ) until a white precipitate formed. The crude product was recrystallised to yield XII, (17.0 g, 52.26%).

XIII: β-(10-phenothiazyl) Propionate Ester

The compound XII (17 g) was dissolved in 1:2 by vol. mixture of ethanol and toluene (700 ml) acidified by addition of conc. sulphuric acid (4 ml) and refluxed overnight. The solution was concentrated (to approximately 50 ml) and diluted by addition of water (500 ml). The crude product was extracted in ethyl acetate (4×200 ml), washed with water, dried over MgSO 4 , filtered and the solvent removed under reduced pressure. White crystals of XIII precipitated from the solution on cooling, (11.85 g, 63.9%).

XIV: β-(10-phenothiazyl) Propanol

A solution of the compound XIII (11.85 g) in dry diethyl ether (33 ml) was added dropwise to a suspension of LiAlH 4 (4.74 g) in dry diethyl ether (70 ml) and stirred overnight at room temperature. Excess LiAlH 4 was decomposed by the dropwise addition of water and filtered. Removal of the solvent under reduced pressure gave the green solid XIV, (5.57 g, 54.7%).

XV: β-(10-phenothiazyl) Propoxy Phosphonic Acid Dichloride

A solution of XXV (1.0 g) and pyridine (1.0 ml) in dry chloroform (60 ml) was cooled to −15° C. A solution of phosphorous oxychloride (4.73 ml) and pyridine (1.0 ml) and dry chloroform (40 mls) was added dropwise over 0.5 h. The reaction mixture was stirred at −15° C. for 2 h and the resulting homogeneous solution allowed to reach ambient temperature over 1.5 h. The chloroform was removed under reduced pressure and the crude product washed with toluene (3×50 ml) to remove any unreacted phosphorous oxychloride affording a green oil XV, (0.9 g, 65.2%).

VIII: β-(10-phenothiazyl) Propoxy Phosphonic Acid

A solution of XV (0.9 g) in deionised water (60 ml) was stirred overnight. The crude product was extracted in ethyl acetate (4×50 ml), washed with water, dried over sodium sulphate. The white crystals that formed were removed by filtration and the filtrate recrystallized a further 3 times to yield the product VIII, (0.301 g, 40%).

Calculated for VIII (C 15 H 16 O 4 NSP): C, 53.43; H, 4.76; N, 4.15; P, 9.19. Found: C, 63.58; H, 5.42; N, 4.77; P, 1.86. 1 H NMR (CDCl 3 ): d 2.24-2.28 (t 2H, J=6.3 Hz); d 3.67-3.70 (t, 2H, J=6.2 Hz); d 4.09-4.12 (t, 2H, J=6.5 Hz); d 6.91-7.19 (m, 8H). 31 p NMR (CDCl 3 ): d 1.69-1.89 (H 3 PO 4 ); d −11.96

(f) nanostructured SnO 2 :Sb films, prepared as described above, were modified by chemisorption of a monolayer of the p-type redox promoter VII, also prepared as described above, from a chloroformic solution (0.02 mol dm −3 ) during 6 h, washed with distilled isopropanol, dried in air and stored in a darkened vacuum desiccator for 24 h prior to use.

(g) A cell, with an internal spacing of about 400 μm, was constructed from a modified TiO 2 film and a modified SnO 2 :Sb film prepared above using a thermoplastic gasket (IPBOND 2025, supplied by Industria Plastica Monregalese). This gasket had an opening at one corner.

(h) The sandwich structure was evacuated in a modified vacuum desiccator, dipped with the opening in the electrolyte solution, and filled by admitting air into the vacuum desiccator. The electrolyte solution consisted of LiClO 4 (0.02 mol dm −3 ) in γ-butyrolactone.

It should be noted that both the LiClO 4 and γ-butyrolactone were carefully purified and rigorously dried prior to use. Finally, the cell was sealed using a UV-curable epoxy resin.

Reagents and conditions for synthesis for Scheme 1 (VIII):

(a) Acrylonitrile, 40% aq. solution benzyl trimethylammonium hydroxide (Triton B), 0° C. (b) Reflux 1 h (c) Methanolic sodium hydroxide, Reflux 15 h. (d) Ethanol, conc. H 2 SO 4 , Reflux overnight. (e) LiAlH 4 , Diethyl ether (dry) (f) Phosphorous oxychloride, stir, −15° C. for 2 h (g) Stir for 1.5 h to bring to ambient temperature (h) H 2 O

(a) Switching Times of Electrochromic (Ec) Window

The rate of colouration of the 2.5 cm×2.5 cm EC window assembled as described in Example 1 was measured following application of a voltage of 1.2 V which biased the viologen modified nanostructured TiO 2 film negative of the phenothiazine modified SnO 2 :Sb film. The colouration time, defined as the time taken for the transmittance to decrease by two-thirds of the difference between the steady-state transmittances in the bleached and coloured states, was about 450 ms. The rate of bleaching of the same EC window was measured by reversing the polarity of the voltage applied to the previously coloured device. The bleaching time, defined as the average time taken for the transmittance to increase by two-thirds of the difference between the steady-state transmittances in the coloured and bleached states, was about 250 ms.

The measured colouring and bleaching times are, as far as the inventors are aware, the fastest switching times reported for EC windows of this area.

(b) Colouration Efficiency of EC Window

The peak and steady state currents of the 2.5 cm×2.5 cm EC window were also measured during colouring and bleaching. The peak and steady-state currents measured on colouring were approximately 10 mA cm −2 and approximately 30 μA cm −2 , respectively. The peak and steady-state currents measured on bleaching the same EC window were approximately 16 mA cm −2 and approximately 1 μA cm −2 , respectively. The colouration efficiency CE(λ) at 550 nm, defined by Equation (1), was determined from the slope of the plot of the increase in absorbance ΔA(λ) versus the charge accumulated in the device ΔQ. The measured CE (550 nm) was approximately 110 C −1 cm 2 .

C ⁢   ⁢ E ⁡ ( λ ) = Δ ⁢   ⁢ A ⁡ ( λ ) Δ ⁢   ⁢ Q ( 1 )

Both the above peak and steady-state currents are very low and suggest that the power consumption of the EC window will be low and that it should have a long-term memory.

Concerning power consumption, the 2.5 cm×2.5 cm EC window prepared in Example 1 will have an associated steady-state current of approximately 30 WA in the coloured state. This implies that the rate of charge consumption is approximately 2.4×10 −3 Cs −1 or approximately 1.5×10 16 electrons s −1 .

Concerning the long-term memory, if a voltage of 1.2 V is applied to the EC window for 60 s and the circuit opened, the EC window first colours and then bleaches on the time-scale of hours. More quantitatively, the absorbance of the EC window measured at 608 nm takes about 3 h to return to the initially measured value, while the time required for the minimum transmittance in the coloured state to increase by 5% is 600 s.

(c) Stability of EC Window

The stability of the 2.5 cm×2.5 cm EC window prepared in Example 1 was tested under ambient conditions by subjecting it to 10,000 electrochromic cycles. Each electrochromic cycle consisted of applying a potential of 1.2 V, which biases the viologen modified nanostructured TiO 2 electrode negative of the phenothiazine nanostructured SnO 2 :Sb electrode, for 15 s and applying a voltage of 0.00 V for 15 s. The parameters used to characterise cell performance were measured after 1, 10, 100, 1,000 and 10,000 electrochromic cycles and are summarised in Table 1.

Another aspect of the stability, is the period over which it is possible to maintain the EC window in a coloured state. This aspect of the stability was examined by applying a voltage of 1.2 V, which biases the viologen modified nanostructured TiO 2 electrode negative of the phenothiazine nanostructured SnO 2 :Sb electrode, and which causes the device to colour. This voltage was applied for 15 s and, having determined that the time required for the minimum transmittance to increase by 5% is 180 s, this potential was applied for 15 s every 180 s. This maintained the EC window in the coloured state throughout. It was found that there was no significant degradation after 500 h.

Generally, the findings summarised in Table 1 establish that a 2.5 cm×2.5 cm EC window assembled as described in Example 1 is relatively stable under ambient laboratory conditions over 10,000 electrochromic cycles while the findings summarised above establish that the same window is stable in the coloured state for 500 h.

Preparation of β-(10-phenothiazyl) Propyl-phosphonic Acid (Illustrated in Scheme 2)

Steps (i)-(v) of Scheme 2 are described in relation to Scheme 1 in Example 1(e).

XVa: β-(10-phenothiazyl) Propyl-phosphonate

β-(10-phenothiazyl) propyl chloride IX (5 g, 1.8×10 −2 M) was refluxed in 5 equivalents of triethyl phosphite for 48 h. The unreacted triethyl phosphite was removed by vacuum distillation to yield the crude product XVa which was taken to the next step without further purification.

1 H NMR (chloroform-d): δ 1.17-1.22 (t, 6H, J=7.1 Hz), δ 1.79-1.92 (m, 2H), δ 2.03-2.13 (m, 2H), δ 3.92-4.14 (m, 6H), δ 6.84-7.17 (m, 8H, aromatic)

XVI: β-(10-phenothiazyl) Propyl Phosphono-trimethyl Silyl Ester

To an ice cold solution of XVa (0.15 g, 4×10 −4 M) in CHCl 3 (dry) was added a cold solution of bromo-trimethylsilane (0.18 g, 1.2×10 −3 M) in CHCl 3 (dry). The reaction mixture was stirred (0° C., 1 h) and then at room temperature for 16 h. The solvent was removed under reduced pressure to yield the crude silyl ester XVI which was taken to the next step without further purification.

1 H NMR (chloroform-d): δ 0.00-0.39 (s, 18H), δ 1.75-1.90 (m, 2H), δ 2.00-2.20 (m, 2H), δ 3.84(m, 2H), δ 6.80-7.20 (m, 8H, aromatic)

XVII: β-(10-phenothiazyl) Propyl-phosphonic Acid,

XVI was stirred in a mixture of 1,4-dioxane: H 2 O (1:1) at room temperature for 2 h. The resulting precipitate was filtered and dried to yield the crude product XVII.

1 H NMR (methyl sulphoxide-d 6 ): δ 1.55-1.67 (m, 2H) δ 1.78-1.84 (t, 2H), s 3.91-3.96 (t, 2H, J=7.0 Hz), δ 6.8-7.3 (m, 8H, aromatic)

Reagents and conditions for synthesis for Scheme 2 (XVI):

(i) acrylonitrile, Triton B (40% aq. solution), 0° C.; reflux 1 h (ii) methanolic sodium hydroxide, reflux 15 h; (iii) ethanol-toluene, conc. H 2 SO 4 , reflux 12 h; (iv) diethyl ether (dry), LiAH 4 ; (v) pyridine-chloroform (dry), phosphorous oxychloride, stir, −15° C., 2 h; stir, RT, 1.5 h; (vi) triethyl phosphite, reflux, 48 h (vii) dry chloroform, 0° C.; bromotrimethyl silane, dry chloroform, 0° C.; stir, RT, 16 h (viii) 1,4-Dioxane/H 2 O (1:1), stir, RT, 2 h.

Preparation of β-(10-phenothiazyl) Propionate Phosphonic Acid (Illustrated in Scheme 3)

XXVI: β-(20-phenothiazyl) Propionitrile

To an ice cold solution of phenothiazine (XXV, 50 g) in acrylonitrile (45 mL) was added Triton B (0.6 mL of a 40% aq. soln.). After some time a vigorous reaction took place. The reaction mixture was heated on a steam bath for 2 h and allowed to cool. The resulting crude solid was crystallized from a 30:70 mixture of hot ethanol and acetone to yield orange crystals of XXVI.

XXVII: β-(10-phenothiazyl) Propionic Acid

The compound XXVI (20 g) was refluxed for 15 h in 450 mL of methanolic sodium hydroxide (methanol:water, 350:105 mL). The crude product was poured into ice water and acidified by the addition of sulfuric acid (2 mol dm −3 ). The crude product was crystallized from ethanol to yield XXVII.

1 H NMR (chloroform-d): δ 2.66-2.67 (t, 2H, J=7.9 Hz); δ 4.04-4.09 (t, 2H, J=7.9 Hz); δ 6.76-7.05 (m, 8H, aromatic)

XXVIII: β-(10-phenothiazyl) Propionic Acid Chloride

XXVII (1.0 g) was refluxed in 10 mL of oxazyl chloride for 3 h. Removal of oxazyl chloride under low pressure afforded the crude acid chloride XXVIII which was taken for the next step without further purification.

1 H NMR (chloroform-d): δ 3.40-3.45 (t, 2H, J=7.9 Hz); δ 4.27-4.32 (t, 2H, J=7.9 Hz); δ 6.87-7.25 (m, 8H, aromatic)

XXIX: β-(10-phenothiazyl) Propionate Phosphate Ester

XXVIII (1.0 g) was dissolved in dry chloroform containing a small quantity of pyridine. Diethyl hydroxy methylphosphonate was added and the reaction mixture was stirred at room temperature overnight. Removal of the solvent under reduced pressure yielded the crude product XXIX which was taken to the next step without further purification.

1 H NMR (chloroform-d): δ 1.32-1.37 (t, 2H, J=7.9 Hz); δ 2.93-2.98 (t, 2H, J=7.9 Hz); δ 4.12-4.28 (m, 6H, J=7.9 Hz); δ 4.41-4.44 (d, 2H, J=7.9 Hz); δ 6.89-7.22 (m, 8H, aromatic)

XXX: β-(10-phenothiazyl) Propionate Phosphono-trimethyl Silyl Ester

To an ice cold solution of XXIX (1.0 g,) in CHCl 3 (dry) was added a cold solution of bromo-trimethylsilane (0.18 g, 1.2×10 −3 M) in CHCl 3 (dry). The reaction mixture was stirred (0° C., 1 h) and then at room temperature for 16 h. The solvent was removed under reduced pressure to yield the crude silyl ester XXX which was taken to the next step without further purification.

1 H NMR (chloroform-d): δ 0.00 (s, 18H); δ 2.93-2.98 (m, 2H); δ 4.23-4.26 (m, 4H, J=7.9 Hz); 67.11-7.19 (m, 8H, aromatic)

XXXI: β-(10-phenothiazyl) Propionate Phosphoric Acid

XXX (0.1 g) was stirred in a mixture of 1,4-dioxane: H 2 O (1:1) at room temperature for 2 h. The resulting precipitate was filtered and dried to yield the crude product XXXI.

1 H NMR (methyl sulphoxide-d 6 ): δ 2.93-2.98 (m, 2H); δ 4.23-4.26 (m, 4H); 6 7.11-7.19 (m, 8H, aromatic)

Reagents and Conditions

(i) Triton B. 0° C., 2 h; reflux 2 h (ii) NaOH, CH 3 N H, reflux 15 h (iii) Oxazyl chloride, reflux 3 h (iv) Diethyl hydroxy methylphosphonate, dry CHCl 3 /Pyrdine, stir r.t. (v) Bromotrimethylsilane, dry CHCl 3 , 0° C., stir r.t. 16 h (vi) 1,4-Dioxane/H 2 O (1:1), stir r.t. 2 h

Preparation of (1-Ferrocenyl) Imido-benzylmethyl Phosphonic Acid (Illustrated in Scheme 4)

XXXII: (1-Ferrocenyl) Imino-benzyldiethylphosphonate

Ferrocene aldehyde (2.5 g, 1.1×10 −2 M) was dissolved in toluene (80 mL). 4-amino benzyl phosphonate (2.6 g, 1.2×10 −2 M) and a catalytic amount of para-toluene sulphonic acid (0.13 g) was added and the reaction mixture was refluxed for 3 h, in a Dean-Stark setup. The solvent was concentrated under reduced pressure, to yield the crude product XXXII which was taken through to the next step without further purification.

1 H NMR (chloroform-d): d 1.25-1.3 (t, 6H, J=7.0 Hz), d 3.13-3.20 (d, 2H, J=21 Hz), d 3.98-4.09 (q, 4H, J=7.0 Hz), d 4.26-4.83 (m, 9H), d 7.12-7.33 (dd, 4H, aromatic), d 8.35 (s, 1H)

XXXIII: (1-Ferrocenyl) Imido-benzyldiethylphosphonate

To a warm (50° C.) solution of XXXII (5.39 g, 1.2×10 −2 M) in methanol (80 mL) was added solid NaBH, (0.5 g, 1.2×10 −2 M). A vigorous reaction occurred and the reaction mixture was refluxed for 3 h. The reaction mixture was cooled to room temperature stirred for 16 h. The solvent was removed under reduced pressure, and the crude product was taken up in chloroform (4×50 mL) and dried. The chloroform layer was washed with water and dried. Removal of the solvent afforded the crude product which was purified using column chromatography (100% CHCl 3 ) to yield XXXIII.

1 H NMR (chloroform-d): d 1.25-1.30 (t, 6H, J=7.0 Hz), d 3.04-3.11 (d, 2H, J=21 Hz), d 3.99-4.05 (q, 4 H, J=7.0 Hz), d 4.05-4.26 (m, 11H), d6.62-6.65 (d, 2H, aromatic), d 7.13-7.16 (d, 2H, aromatic)

XXXIV: (1-Ferrocenyl) Imdio-benzyldiethyl Trimethylsilyl Ester

To an ice cold solution of XXXIII (1.0 g, 2×10 −3 M) in CHCl 3 (dry, 10 mL) was added a cold solution of bromo-trimethylsilane (2.0 g, 1.3×10 −2 M) in CHCl 3 (dry, 4 mL). The reaction mixture was stirred (0° C., 1 h) and then at room temperature for 16 h. The solvent was removed under reduced pressure to yield the crude silyl ester XXXXIV which was taken to the next step without further purification.

1 H NMR (chloroform-d): d 0.00 (s, 18H), d 2.94 (d, 2H, J=21 Hz), d 4.17-4.19 (m, 11H), d 6.79-6.85 (d, 2H, aromatic), d 7.09-7.20 (d, 2H, aromatic)

XXXV: (1-Ferrocenyl) Imido-benzylmethyl Phosphonic Acid

XXXIV was stirred in a mixture of DMF/H 2 O (1:1) at room temperature for 4 h. The crude product that precipitated was filtered, washed with H 2 O and dried under vacuum to yield XXXV.

1 H NMR (methyl sulphoxide-d 6 ); d 2.71-2.78 (d, 2H, J=21 Hz), d 3.93-4.2.6 (m, 11H), d 6.53-6.55 (d, 2H, J=7.9 Hz), d 6.92-6.9.5. (d, 2H, J=7.1 Hz)

31 P NMR (methyl sulphoxide-d 6 ): d 24.4

Reagents and Conditions

(i) Toluene, para-toluene sulphonic acid, reflux 4 h (ii) Sodium Borohydride CH 3 OH, reflux 3 h (iii) Bromotrimethylsilane, dry CHCl 3 , 0° C., 0.5 h; r.t. 12 h (iv) Dimethylformamide/H 2 O (1:1), r.t. 4 h

Preparation of 6-(10-phenoxazyl) Propionate Phosphonic Acid (Illustrated in Scheme 5)

XIX: β-(10-phenoxazyl) Propionitrile

To an ice cold solution of phenoxazine (XVII, 50 g) in acrylonitrile (45 mL) was added Triton B (0.6 mL of a 40% aq. soln.). After some time a vigorous reaction took place. The reaction mixture was heated on a steam bath for 2 h and allowed to cool. The resulting crude solid was crystallized from a 30:70 mixture of hot ethanol and acetone to yield orange crystals of XXX.

XX: 6-(10-phenoxazyl) Propionic Acid

The compound XIX was refluxed for 15 h in 450 mL of methanolic sodium hydroxide(methanol:water, 350:105 mL). The crude product was poured into ice water and acidified by the addition of sulfuric acid (2 mol dm −3 ). The crude product was crystallized from ethanol to yield XX.

1 H NMR (chloroform-d): δ 2.74-2.80 (t, 2H, J=7.9 Hz); δ 3.90-3.96 (t, 2H, J=7.9 Hz); δ 6.54-6.88 (m, 8H, aromatic)

XXI: β-(10-phenoxazyl) Propionic Acid Chloride

XX (1.0 g) was refluxed in 10 mL of oxazyl chloride for 3 h. Removal of oxazyl chloride under low pressure afforded the crude acid chloride XXI which was taken for the next step without further purification.

1 H NMR (chloroform-d): δ 3.19-3.28 (t, 2H, J=7.9 Hz); δ 3.90-3.99 (t, 2H, J=7.9 Hz); δ 6.47-6.90 (m, 8 H, aromatic)

XXII: β-(10-phenoxazyl) propionate phosphate ester

XXI (1.0 g) was dissolved in dry chloroform containing a small quantity of pyridine. Diethyl hydroxy methylphosphonate was added and the reaction mixture was stirred at room temperature overnight. Removal of the solvent under reduced pressure yielded the crude product XXII which was taken to the next step without further purification.

1 H NMR (chloroform-d): δ 1.35-1.42 (t, 6H, J=6.9 Hz); δ 2.77-2.82 (d, 21, J=7.3 Hz); δ 3.91-3.96 (d, 2H, J=7.6 Hz); δ 4.11-4.28 (m, 4H); δ 4.41-4.44 (d, 2H, J8.8 Hz), δ 6.55-6.87 (m, 8H, aromatic)

XXIII: 6-(10-phenoxazyl) Propionate Phosphono-trimethyl Silyl Ester

To an ice cold solution of XXII (1.0 g,) in CHCl 3 (dry) was added a cold solution of bromo-trimethylsilane (0.18 g, 1.2×10 −3 M) in CHCl 3 (dry). The reaction mixture was stirred (0° C., 1 h) and then at room temperature for 16 h. The solvent was removed under reduced pressure to yield the crude silyl ester XXIII which was taken to the next step without further purification.

1 H NMR (chloroform-d): δ 0.0 (s, 19H); δ 2.65-2.70 (t, 2H, J=7.6 Hz); δ 3.80-3.86 (m, 2H); δ 4.25-4.36 (t, 2H, J=10.0 Hz); δ 6.44-6.80 (m, 8H, aromatic)

XXIV: P-(20-phenoxazyl) propionate phosphonic acid XXIII (0.1 g) was stirred in a mixture of 1,4-dioxane: H 2 O (1:1) at room temperature for 2 h. The resulting precipitate was filtered and dried to yield the crude product XXIV.

1 H NMR (methyl sulphoxide-d 6 ): δ 2.60-2.67 (m, 4H), δ 3.66-4.20 (t, 2H, J=7.0 Hz), δ 6.49-6.86 (m, 8H, aromatic)

31 P NMR (methyl sulphoxide-d.): 24.5

Reagents and Conditions

(i) Triton B. 0° C., 2 h, reflux 2 h (ii) NaOH, CH 3 OH, reflux 15 h (iii) Oxazyl chloride, reflux 3 h (iv) Diethyl hydroxy methylphosphonate dry CHCl 3 Pyridine, stir r.t. (v) Bromotrimethylsilane, dry CHCl 3 , 0° C., stir r.t. 16 h (vi) 1,4-Dioxane/H 2 O (1:1), stir r.t. 2 h

Stability Tests

Preparation of Nanostructured Electrodes:

All glass was thoroughly cleaned prior to use. Each sheet was manually cleaned using detergent which was thoroughly rinsed off using water. This was then washed with acetone to remove all water present and the acetone was evaporated using hot air. Each film was deposited using a doctor-blading technique. An adhesive stencil was placed over each glass electrode giving the required geometry necessary to leave a perimeter of 5 mm. The glass surface was cleaned with iso-propanol and air-dried prior to deposition. A deposit of sol was placed at one end of the glass and manually drawn to the opposite end of the glass with a glass rod (7 mm diameter) leaving an even deposit of the sol. The cathode was a 50 mm×50 mm square TEC 15 glass sheet with nanoporous nanocrystalline titanium dioxide (prepared as in Example 1 (a) except that the films were dried with hot air and sintered in air for 1 h) coated on an area of 40 mm×40 mm square at the centre of the window, leaving an exposed one half centimeter perimeter for sealing materials. The anode was a 50 mm×50 mm square TEC 15 glass sheet with nanoporous nanocrystalline antimony doped tin oxide (prepared as in Example 1 (d) except that the films were dried with hot air and sintered for 1 h) coated on an area 40 mm×40 mm square at the centre of the window, leaving an exposed one half centimeter perimeter for sealing materials.

Modification of Nanostructured Electrodes

Prior to being modified with the redox compound, the nanostructured cathodes and anodes were placed in an oven at 350° C. to remove any water vapour or organic material. The electrodes were allowed to cool to approximately 80° C. before being placed into the redox compound solutions. All cathodes consisting of a nanostructured TiO 2 working electrode where modified by chemisorption of the viologen bis-(2-phosphonoethyl)-4,4′-bipyridinium dichloride from an aqueous solution (1×10 mol dm −1 ) containing 0.1 M LiClO 4 over a 2 h period. Following the derivatisation process, each film was placed horizontally in a wash bath of ethanol for one minute. The washed, derivatised electrodes were dried using hot air.

All anodes consisting of antimony doped tin oxide electrodes were derivatised with a series of six redox promoters giving six sets of six windows as outlined below:

Set A: No redox promoter chemisorbed onto the antimony doped tin oxide electrodes Set B: A solution of 6-(10-phenoxazyl) propionate phosphonic acid as prepared in Example 6 (ca. 1×10 −1 M in acetonitrile and 6×10 −3 M LiPF 6 ) were prepared and six windows were immersed for two hours in this solution. Set C: A solution of Z-(10-phenothiazyl) propoxy phosphonic acid as prepared in Example 1(e) (ca. 1×10 −3 M in acetonitrile and 6×10 −3 M LiPF 6 ) was prepared and six windows were immersed for two hours in this solution. Set D: A solution of B-(10-phenothiazyl) propyl-phosphonic acid as prepared in Example 3 (ca. 1×M in chloroform and 6×10 M LiPF 6 ) was prepared and six windows were immersed for two hours in this solution.

Set E: A solution of 6-(10-phenothiazyl) propionate phosphonic acid as prepared in Example 4 (ca. 1×10 −3 M in chloroform/acetonitrile (4:1) and 6×10 −1 M LiPF 6 ) was prepared and six windows were immersed for two hours in this solution.

Set F: A solution of (1-ferrocenyl) imido-benzylmethyl phosphonic acid as prepared in Example 5 (ca. 1×10 −3 M in 1:1 chloroform:dimethyl sulfoxide and 6×10 −3 M LiPF 6 ) was prepared and six windows were immersed for two hours in this solution.

Following the derivatisation process, each film was placed horizontally in a wash bath of the respective solvent it was modified from, for one minute. The washed, derivatised electrodes were dried using hot air. The windows were sealed immediately after dying. The cathode and anode were sandwiched together with the electrodes placed in an offset configuration with 2-3 mm offset on two opposite sides to provide an area for an external ohmic contact.

The switching times and stability of each device (A-F) were tested as described in Example 2. The results are shown in Tables 2-7. Optical absorption spectra were recorded using a Hewlett-Packard 8452A diode array spectrophotometer. A Solartron SI 1287 potentiostat was used to record potential-current characteristics. All reported testing was done at room temperature.

The tabulated results can be explained as follows:

Transmittance in the bleached state (%)—the percentage of light passing through the device in the colourless state. Transmittance in the coloured state (%)—the percentage of light passing through the device in the coloured state. Steady State Current (SSC)— the value of the current when it has reached an equilibrium.

Generally, the findings summarised for A-F in Tables 2-7 establish that a 40×40 mm EC window assembled as described above is stable under ambient laboratory conditions over 7000 electrochromic cycles. The values of the transmittance in the colourless state are generally consistent throughout each test indicating that a large proportion of the incident light is passing through each device even after 7000 cycles. This indicates substantially no optical degradation of the films. The transmittance values in the coloured state are also generally consistent. The dynamic ranges between the transmittance in the colourless state and the transmittance in the coloured state are large which indicate good performance for an EC device. The SSC values for the coloured state are generally less that 25 micro amps cm −2 . This indicates a very small leakage current. The SSC for the bleached state in each case is of the order of 1 micro amp cm −2 These low power consumption readings illustrate the memory effect of the devices as constructed. Furthermore, each device exhibits rapid switching times for both the coloured and colourless states. Colouring times range from 30 to 75 ms/cm 2 and bleaching times from 25 to 50 ms/cm 2 . These times are significantly faster than those obtained with conventional devices which have switching times of at least 1 s/cm 2 .

The advantages of the EC devices of the invention over previous EC devices are:

1. They are fast switching. 2. They provide deeper colouration. 3. The range of colours is greater. 4. They have low steady state current.